Aromatic polyamides having new helical structures were synthesized by combination of optically active dissymmetric joints, such as biphenylene and binaphthlene, with aromatic hard segments, such as phenylene and 4,4'-azophenylene. CD spectra of the polymers obtained that the helical structures are stable up to 120℃ in a polar solvent, and the structures were maintained in strong acids such as methanesulfonic asid. A polyamide that contains azobezene moieties in the main chain was transformed on irradiation of UV light because of trans-cis photoisomerization of the photosensitive moieties. This polymer can be use as a nonlinear optical material. The preparative method was applied to preparation of similar polyesters, polyurethanes, and polyamines.